Method of preparing dicyandiamide



Feb. 25, 1947. J L, @BORNE I2,416,542

METHOD OF PREPARING DIGYANDIAMIDE Filed Dec. 19, 1944 INVENTOR da fw. afin/wf.

' BY ie@ @www ATTORN EY Patented Feb. 25, 1947 Y METHODOE PREPARING DIoYANDIAMrDE 1 John L. sborne, Elizabeth, N. J.; assig'nor'to American vCyanalvnd Company, Nl Y.,' a corporation of Maine New York,

` l' Aprl'ieatin Deeinter 19,1944, serialnNojsesQsz" f This invention relates to. a process of preparing dicyandiamide, from crude'calciumA cyanamide. The principal objectI of the present invention is to prepare dicyandiamide `by polymerizing cyanamide obtained from crude calcium cyanamide in an efficientl manner and in good yields and purityy while supressing the formation of undesirable by-products. l An important adjunct of the invention resides in facilitating contact between a gaseous precipitant such as CO2 'with calcium cyanamide such' as by use of what may be termed a ICO9 carrier, that is, by the use cfa material which will react'with CO2 and the resulting carbonate or bicarbonate go into solution, where it will then readily react' with'CaCNz. Such a situation makes possible a better contact of the gaseous precipitation agent with the calcium cyanamide' than if such agent were used strictly in gaseous form, and consequently can result in a saving of up to 25% of theCOz. t

In patent application Serial No. 568,893 it is' proposed to carry out a process substantially identical with that of the present application. employing the methyland ethylamines as the CO carrier. In Serial No. 568,894 guanylurea and guanylurea carbonate are employed, and in Sei rial No. 568,895 the ethanolamines are employed.

, Heretofore, as disclosed in the prior art, carbon dioxide has been used to precipitatecalcium carbonate from aqueous slurries of crude calcium cyanamide. However, such processes involve, essentially, gaseous-liquid reactions'. When pure carbon dioxide is used, such reactions necessitate bulky, expensive and unusually complex mixing and diffusion apparatusfin order to comminute the carbon dioxide bubbles and elect a better contact of the carbon dioxide and liquid solvent. When stack gases are used as a source of carbon dioxide in these prior processes, `the disadvantages become still greater, for then the use f gaseousliquid reactions in the preparation of cyanamide and dicyanamide necessitates the processing of large volumes of gases. Th'isrequires unusually large, bulky equipment and ne-v cessitates treatment over extended time inter? vals. The operation of such processes `as disclosed in the prior art is accordingly' 'quite in-. efcient, principally because ofthe low solubility of carbon dioxide in water. these prior processes also fail to Vovercome the disadvantages attendant upon the low solubility of lime and calcium cyanamide in the waterA used to make up .the aqueous slurry.

` The present process involves a novelv method' 4 claims. (C1. 23-190) of facilitating the reaction between carbon, di oxide and crude calcium cyanamide slurries'.l ItP relates to a simple process for bringing about the better solution of carbon dioxide in the wa-iV .ter forming the slurry. Thus, it has been found that by the addition of a suitable water Soluble' compound capable of carrying carbon dioxidejiri combinationthere is eflected what is essentially a marked increase 4in the solubility of carbon `til-, oxide. Furthermore the reaction of ACO2 and calk cium cyanarnide is' completed more efliciently. This is due to .the fact that th'e process is eiected as a liquid to liquid rather than as a gas to lid-fj uid type of reaction. [The solubilizing of the car-: 1 bon dioxide converts vthe latterinto a more readl ily available condition, diffused throughout the. liquid, and hence effects the reaction as one, closely approximating an ideal liquid to 'liquid type of Contact. l l j These novel features in the process of the; present invention make possible the use of small-Q er, less complicated apparatus.V The present` process valso shortens thetime necessary to corn-z plete the reaction of .carbon dioxide with thef lime and the' CaCNz. Atthe same time it makes'` possible the useof lower pressures orcarbon dioxide while eifectingfa greater'concentrationj ci' carbon dioxide in solution. YThis re'sultsrinY a more eiiicient process and a more uniform 'qual-Qi ity of product. Among the compounds capable of reacting in this manner are the followingtl the alkali metal carbonates, such as sodium and; potassium carbonataguanidine and guanylurea' both as such and as their carbonates, the ethanolamines such as the mono, di andtri forms, andf also the alkyl aminesvsuch as .the mono` and poly.' methyland ethyl amines.

More specicall'y, in accordance with one emi-Q bodiment of this invention, it is proposed that.

soda ash be dissolved in `the liquor used to ex-. f tract vcyanamide from the crude calcium ,Cyifn--;`

-`amideslurry andthai-l carbon dioxide be' passedV 1,101'.` This yields calciumcarbonate' as a precipisure. Q an additional time interval in a second tank to increase the .extraction of the calcium cyanamide after which the slurry is filtered. In order to .increase the concentration `of nitrogen present in I the form of cyanamide and later as dicyandiatate and sodium acid cyanamide and/or free w cyanamide. This solution may be then concentrated Yas by evaporation, and' any cyanamide therein not already polymerized, polymerizes to form dicyandiamide which is readily extracted by filtration. e

It is to be noted that the use of the process of this invention not only makes possible a greater i concentration of carbon dioxide in the slurry but also results in the presence ofy carbon dioxide in a more readily reacting form than the usual gaseous state.` This is due to the addition to the slurry of the above mentioned compounds. All of these compounds have a high alnity for .car-

e bon dioxide which isheld in combinationrthere'- with. Hence'thesel are capable of serving as Vcarriers of carbon1dioxide held .in combination and l readily available forV further reaction as lwitl'ithe calcium of the slurry. These compounds .make l possible a more complete absorption and solution of `carbon dioxide in the mother liquor than could be effected ,if the carbon dioxide were bubbled through a slurry containing `no such carrier compounds. Furthermore with these compounds present, the carbon dioxide need be under little or no pressure in order to `obtain a high concentration of available carbon dioxide. Heretofore equally high Vconcentrations of carbon dioxide could be attained only by using carbon dioxide under several atmospheres pressure. Because of the low pressure solubilizing step characteristic `of the process of this invention, it is unnecessary to carry out the process in such expensive air-tight autoclaves and pressure vessels as here- The accompanying ow sheet diagrammaticaldecomposition due to side reactions which result 3 in the production of NH3', urea and the like. The slurry maybe prepared in an atmosphere of Vcari bon dioxide under superatmospheric pressure in an autoclave or, alternatively, carbon dioxide is i bubbled through the slurry at atmospheric pres- The reactants are mixed, preferably, for

mide, the mother liquor forming the clear filtrate i Vis recycled a number of times and reslurried with additional portions of crude calcium cyanamide,

the combined recycled mixture being then finally l filtered. vWhen the mother liquor attains its op- `by scraping the filter plates clean of the spent sludge. A new slurry is then prepared as above described, theY cycling and recycling steps are carried out again terminating in a final iiltration and removal from the extraction cycle of the mother liquor containingits optimum concentration of cyanamide or dicyandiamide. This optimum concentration may lbe one either low in cyanamide and high in dicyandiamide or the reverse. The former situation is a highly desirable one inasmuch as by building up'the content of dicyandiamide in the mother liquor, that is,

vby'polymerization of the cyanamide to dicyandiamide, as the former is freed from calcium cyytmamide, the liquor going through the by-pass will contain more and more dicyandiamide making evaporation at this stage unnecessary. That dicyandiamide can be built up in the mother liquor will be apparent when it is considered that the liquor at this stage is of suiciently high alkal-inity .and temperature to facilitate polymerization of the cyanamide to dicyandiamide. This situation will bemore fully discussed hereinafter.

In addition to the .above batch process, the process can be readily effected by continuously drawing oi a fractional part of the mother liquor or concentrate through the by-pass for further special treatment. The remaining portion is returned or recycled to the first tank where more crude calcium cyanamide and carbon dioxide as Well .as wash liquor and mother liquor from other sources, as shown, can be added to maintain the recycling volume constant.

The mother liquor withdrawn through the bypass may be concentrated in an evaporator, preferably by low temperature vacuum distillation, to remove the excess water. The carbon dioxide held in combination by the carrier is simultaneously evolved with the result that the alkalinity of the solution may be increased to that of a solution having a pH of 11.0' or thereabouts, whereupon practically all of the cyanamide polymerizes to dicyandiamide. containing. perhaps a small yamount of cyanamide inthe entrained liquor, is readily separated out by cooling and ltering the solution. The mother liquor forming-the filtrate is recycled as shown to forma new slurry. VIf contaminated unduly with decomposition products, such as ureav for example, it may be preferable to discard this 'ltrate periodically.

When vacuum evaporation of the by-passed mother liquor is conducted at a low temperature, i. e., about 30 C. to 35 C., most of the cyanamide present polymerizes to form dicyandiamide due to the high alkalinity of the solution. Any remaining free cyanamide subsequently polymery izes on storage. However, if complete conversion of the cyanamide to dicyandiamide is desired immediately, the evaporation step may be omitted, particularly if the solution is stronger timum concentration of cyanarnide or dicyandiamide, it is withdrawn through the by-pass for 1 further treatment. After a predetermined numl ber of recycling steps including the reslurrying of the lter cake, the lter cake remaining as i a sludge in'i'the final filtration step is washed with a small amount of Wash liquor in order to remove 3 the greater ,portion of the entrained carbon dioxide carrier left therein. This wash liquor is rel cycled to form an aliquot part4 of a new batchr .f or slurry of calcium cyanamide. maining in the iilter `is removed kfrornthe systenfiV The sludge 'ree sary to evaporate it further.

than about 10 or 12%. Thus, if the solution has a concentration of 15% or higher, it is not neces- Instead polymerization can be carried out by a carefully controlled heating step here which effects a conversion of the cyanamide to dicyandiamide. The dicyandiamide separates out in crystalline form and is easily collected by cooling the liquor and 'ltering as above described. i

In connection with the building. up of dicyandiamide in the mother liquor at the expense of the cyanamide, and prior to by-passing `the mother liquor to the recovery systemV as above The dicyandiamide',

5 set forth, the following is an important consideration, f

It would of course, be ydesirable to operate the cycle under such conditions that most, if not all, of the cyanamide went directly to dicyandiamide reasonably as fast as the cyanamide was freed, maintaining enough water in the system to keep the dicyandiamide in solution so that when the nal liquor reached the evaporator the dicyandiamide could be recovered therefrom either by evaporation or chilling or both.

The above may be readily accomplished by maintaining the pH of the system at 7.0 or above. While high temperatures are desirable in order to increase the rate of polymerization of cyanamide to dicyandiamide, yet the temperature is not as important as the pH.

It will be apparent that as the calcium cyanamide is fed to the mixing tank the pH has a tendency to rise, whereas when the CO2 is fed to the mixing tank the pH has a tendency to fall. Thus, it is a simple matter, by judicious control `of these two reactants, to maintain the pH between 7.0 and 12.0 so as to maintain desirable cyanamide polymerizing conditions. This can be' very simply accomplished by keeping the calcium cyanamide feed ahead of the carbon dioxide feed. The temperature kof the extraction cycle may be maintained at from 30 C. to boiling, the exact gure depending upon the existing pH. For a given pH within the desired range, .the higher the temperature, the faster the polymerization. At the same time, if operating conditions require a stated temperature, the pH may be adjusted accordingly. Y For instance, where the temperature of the reaction mass is 50 C. cyanamide may be readily converted to dicyandiamide at a pH of 9.6 while at higher temperature such as 80 C. the optimum pH is about 9. At boiling temperatures the pH may drop as low as 8 while still obtaining polymerization of cyanamide to dicyandiamide at good rates.

The increase in temperature to increase the rate of polymerization can be very easily accomplished where flue gases are used as a source of carbon dioxide since such gas asdischarged from a boiler plant will generally be at a temperature of 204 C. or higher. Thus the sensible heat of such gases may be used Vto raise the temperature of the reaction mass and to supplement if necessary the heat evolved there. In the event that the temperature in the mixing tank tends to rise toundue heights, this canbe readily con-.- trolled by proper cooling of the stack gases. Inasmuch as such gases contain carbon dioxide generally to the extent of about 12%-, the other constituents being in the nature of diluents, a large volume of gas may be passed through the magma in the mixing tank so as Vto accurately control the temperature desired there.

Generally speaking, optimum quantities of cyanamide may be released from a calcium cyanamide slurry in the presence of CO2 Vwhere vthe pH is maintained no lower than '7.0 and preferably from 8.0 to 11 or slightly higher with a temperature of from 30 C. to boiling. A rise in temperature for any given pH will, of course, increase the' speed of polymerization and as the temperature rises the pH may be decreased toward 7.0 while still maintaining the same polymerization rate. '.Under these circumstances, it is desirable to'maintain sufhcient water in the systemto keep all of the dicyandiamide formed in solution plus a slight excess so that there will be no loss of Y 6 dicyandiamide values: expected temperaturedrop of the mother liquor asit passes through the lter.

4Thus it is entirely possible to maintain the cycle under such conditions of pH and temperature that there will be little or no cyanamide going through the by-pass but on the contrary this by-passed mother liquor vwill be almost exclusively a desirably high concentration ofaqueous dicyandiamide solution containing a minimum quantity of undesirable decomposition products such as urea. Under `these circumstances, a simple evaporation and/0r chilling will precipitate dicyandiamide from such clear'solutions-in good purity which may be filtered .from the mother liquor and recovered as such. mother liquor from the dicyandiamide'recovery system may then bereturned to the dioated.

Only a smallv amount of the carrier is 'lost from the system by failure to Wash the rst ylter cake. Another small portion of thecarrier may be lost by failure to wash the final lter'cake. However, by flushing these lter cakes with wash Water the carrier therein is easily removed., Thus, the entrained carrier may be removed from the final product by washing it out of the iilter cake with a small portion of water and simultaneously leaving the relatively insoluble dicyandiamide on the lter. Hence it is .unnecessary to renew the entire supply of the carrier for each extraction. Instead, the addition `of a small .portion of the carrier or an aqueous solution thereof to the re-" cycled mother liquor at intervals during the process or after each extraction cycle is ample to increase the concentration of the carrier inthe mother liquor sufficiently for effective re-us'e upon further addition of carbon dioxide.

Due tothe inclusion of a lter in the extraction and/or conversion cycle,'the solids are being continuously removed. Thusany desirable concen-v tration of solubles up to and just short of saturation in the liquor for any desirable working tem-l perature may be had without making the recycle magma unhandlable due to solids.

y The reactions involved may be briefly represented by the following equations when sodium carbonate is used as thecarbon dioxide carrier:

The sodium bicarbonate formed serves as a highly accessible source of carbon dioxide and reacts with the' crude calcium cyanamide to precipitate calcium carbonate as follows: p

caCN2+2NaHco3 oaCo3+H2CN2+Na2co3 Sodium carbonate is thus reformed andis in condition to react immediately with the incoming carbon dioxide to give the bicarbonate and con'- tinue the precipitation of more calcium.'

The corresponding equations occur when po-4 Example 1 1000 parts of water, 250 parts of crude calcium cyanamide and 70 parts of sodium carbonate are worked up into a slurry and sufficient Ycarbondioxide, say 125` parts, added thereto to '.precipi-r tate the Y.calcium andro-react with the-sodium" during the normal and` The.

cycle a's inenana temperature below 35 3C., cooled, and, the crystalline precipitate, predominantly dicyandiarnide contaminated with such small amounts of cyanamide as are present in the entrained liquor, recovered by filtration,

VExample Z Example 1 is repeated carrying out the eVaporation stepY at a higher temperature which results; in practically pure dicyandiamide being obtained. u Thus, when evaporation is effected at a higher temperature in thev rangeV of about 60 to` 80 C., or higher the cyanamide polymerizes yielding practically 100% dicyandiamid'e which precipitates out of solution and is readily sep- -arated by cooling and filtering. The-ltrate comprising mother liquor containing sodium carbon'- ate is recycled to form a. new batch or slurry of calcium cyanamide.

Example 3 100'parts of crude calcium cyanamide are gradjually fed into a300 part Ymixture Yof wash water1 containing sodium bicarbonate andfmother 'liquor containing sodium carbonate from a lprevious batch extraction. The vslurry is fortified with about 5 to 10 parts of sodium carbonate and 50 v.parts of carbon dioxide are simultaneously supplied while maintaining the pH at 8.4 and keeping/the temperature below 35 C. The resulting slurry is passed pto another mixing kettle and v. thenv filtered. About 275 parts of filtrate are obtained containing from 10% Vto 12% of cyanamide. Theysludgeton the filter is Washed `and the wash water-recycled to form part of a new batcl'.` Y Due tothe low'concentration of values t Example `4 I A batch similar to that described in Example 3 l is subjected to the same series of steps to obtain acorresponding 275 partV filtrate. In order to obtain apractically complete conversion to dicyandiamide, the'solution o f cyanamide comprising the 275 part filtrate is evaporated at a temperature of about 70 C., althoughl othertemperatures can also be used up to boiling. K A highly alkaline scdiumcarbonate solution is formed by Y the evolution of CO2 from the sodium bicarbonate solution. This results rin a solution having a pH between 8.4*and 11.4, when the: higher temperatures above given are used to accelerate the Ypoly:nerization, ofthe cyanamide toA dicy'andi-r amide. Since the latter is relatively `insoluble in the cooled motherl liquor, the dicyandiamide is readily separated byfiltering the crystalline precipitate. The filtrate is then recycled to form another slurry of calcium cyanamide for subsequent extraction. y f

' The extractionstep of the p-rocess described in the preceding examples is preferably carried out at alpH of approximately 8:4. Various changes y mayghowever, be made: in. the Vparticularv steps;`

thus for example.; if stack' gases are used as'the source of carbon dioxide it may be preferable to Y strip the CO2 from the staok'gases with an aqueous solution of a carrier and thereafter admix the carrier solution with the slurry, thereby precipitating CaCOg, the whole mixture being led directly into the rst mixing tank.

A feature of this invention is the relativelyfcomplete control of the process and the relatively rapid initiation of the reaction obtained by the use of sodium carbonate or a similar CO2 carrier.V

In the ill-ustrative examples sodium carbonate solutions of 1.0 AN up to 3.0 N or more proved to be highly effective.

When the above examples are repeated without the use of a CO2 carrier substantially longer periods of time are required to effect the calcium precipitation. Also due to the lesser speed of absorption of. CO2 without the carrier, proportionately more CO2 is required because more CO2 passes through the slurry unabsorbed.

' In ther examples given, KzCOa, guanidine or guanylurea, either as such or as their carbonates, or an ethanolaminefor alkyl amine can be used in place of sodium carbonate. dilute solutions of the respective carbon dioxide carriers of from 3% to 5% or even 10% strengt fall in a desirable range. Y. What is claimed: 1. A method of preparing dicyandiamide which includes slurrying CaCNz in the presence of CO2 and a substance chosen from the group consisting of Na2COa and KzCOa, in suicient water to maintain al1 the dicyandiamide formed in solution, maintaining a pH betewen '7.0 and 12.0 and a temperature between 30 C. and boiling, whereby the CaCNz is converted to CaCO; and dicyandiamide, separatingthe CaCOs from the mother liquor, Vand Vrecovering'the dicyandiamide from kthe latter.

2. yiifmethool of preparing dicyandiamide which includes slurrying CaCNzin the presence of CO2 and a substance chosen from the group consisting of YNaeCOa and KzCO, in suflcient water to maintain all the dicyandiamide formed in so-lution, maintaining a pH'between '7.0 and 12.0 and a temperature between 30 C. and' boiling,.where by the CaCNz is converted to CaCOa and dicyandiarnide, separating the CaCO3 from the mother liquor, recirculating the mother liquor vuntil it is just. short of saturation with clicyandiamide, and recovering the dicyandiamide therefrom.

' 3. A methodof preparing dicyandiamide which includes slurrying CaCN2 in the presence of CO2 and NazCOs, with suiicient water to maintain all the dicyandiamide formed in solution, maintaining the pH of the slurry at from 7.0 to 12.0 and a temperature between 30 C. and boiling, filtering out the solids, recirculating the mother liquor with fresh additionsof CaCNz and` CO2,

, until the mother liquorfrom the lsolids removal isl just short of saturation with 'dicyandiamida vand recovering the dicyandiamide therefrom.

4. A method of preparing dicyandiamide which In each instance- 9 recirculating the dicyandiamide mother liquorvto UNITED STATES PATENTS the cycle. A Y

Number Name Date JOHN L' OSBORNE' 2,337,488 Osborne Dec, 21, 1943 REFERENCES CITED 5 OTHER REFERENCES The following references are of record in the K Me110rC0mpI`ehEnSiVe Treatise 0n 11'10182'1110 le of this patent: and Theoretical Chemistry, v01. 2, Vpage 763.

(Copy in Division 59.) 

